Anal. Calcd. for C1,HlpBrNO: C, 56.5; H, 3.6. Found: C, 58.3; H, 3.9. A solution of 0.5 g. of the amino ketone in 10 ml. of dilute hydrochloric acid was treated at 10” with 0.2 g. of sodium nitrite, allowed to stand for ten minutes, and then heated t o boiling. The resulting 3-bromofluorenone separated from alcohol in the form of yellow plates (0.3 g.), m. p . 161-162’.
SCHOOL OF CHEMISTRY UNIVERSITY OF MINNESOTA MINNEAPOLIS, MINNESOTA RECEIVED AUGUST5, 1944
The Stereochemistry of Cobbation Number Eight. Corrections BY LOUISE. MARCHI
Attention has been called to several serious errors which appeared in “The Stereochemistry of Cotirdination Number Eight.”l On page 331, in the right hand column, the sixth line from the bottom which reads 3- CD EF should be deleted, since it is an obvious repetition of the line above it; the seventhline from the bottom should read 2AB CD E F instead of 3AB CD EF, since the latter is not a member of a class of coordination number eight. In Table IV, page 332, the isomer numbers for Class AB, 6c, Conftguration C, should be: Optically active, 0; Optically inactive, 1; Total, 1, instead of Optically active, 2; Optically inactive, 0; Total, 2. In the same table, on page 333, the isomer numbers for Class 3AB 2c, Configuration C, should be: Optically active, 14; Optically inactive, 2; Total, 16, instead of Optically active, 20; Optically inactive, 0; Total, 20.
so unreactive. For although the above-mentioned workers have also shown that branching of the chain reduces reactivity by as much as 100%, their data indicate that i-amyl chloride would have reacted with the iodide to an extent of 50% under the same conditions of time and temperature (twenty-four hours and 60’). The possibility that the i-butyl compound might have rearranged during distillation to the more unreactive t-butyl chloride was eliminated by refractive index measurements; found, n% l.$oOo; known, 1.40096.2 (2) Timmermans and Martin, J . chim. phys., PS, 747 (1926).
DEPARTMENT OF CHEMISTRY ILLINOIS INSTITUTE OF TECHNOLOGY CHICAGO, ILLINOIS RECEIVED JULY 17, 1944
3,5-Diiodo-4-(4’-hydroxyphenosy)-hippuric Acid and 3,5-Diiodo-4-(3‘,5‘-diiododf-hydroxyphenosy)-hippuric Acid BY CARLNIEMANNAND G . E. MCCASLAND
In the course of testing a series of reactions in order to determine their usefulness for the synthesis of thyroxine containing peptides 3,sdiiodo-4-(4’-hydroxyphenoxy)-hippuric acid and 3,5-diiodo-4-(3’,5’-diiodo-.l’-hydroxyphenoxy)-hippuric acid have been prepared and characterized.
.-
3,5-Diiod0-4-(4~-acet~qphenoxy)-benzoic Acid (I) To 10 g. of recrystallized 9,5-diiodo-4-(4’-hydroxyphenoxy)-benzoic acid,’ m. p. 259-60°, was added 40 ml. of acetic anhydride and 2-3 drops of concentrated sulfuric acid and the mixture heated at 100’ for thirty minutes. The solution was cooled, poured into ice water and, after decomposition of the acetic anhydride, the colorless solid, (1) MPrcbi, TXISJOURNAL, 66,329-333 (1943). which had separated, was collected, washed and dried zn vacuo. The crude product (10.8 9.) was twice reMONSANTO CHEMIW COMPANY crystallized from absolute ethanol t: give 9.6 g. (890jc) CEPTRAL RESEARCH DEPARTMENT, UNIT 111 of I, colorless needles, m. p. 231-232 . DAYTON, OHIO RECEIVED JULY 18, 1944 Anal. Calcd. for C16HlaO6It (524): C, 34.4; H, 1.9; I,48.4. Found: C, 34.7; H, 2.1; I, 48.8. The Reaction of Alkyl Halides with Potassium Ethyl 3,5-Diiodo-4-( 4’-acetoxyphenoxy)-hippurate (11). Iodide To 3.1 g. of I suspended in 20 ml. of dry benzene was added 1.35 g. of phosphoru: pentachloride and the mixture BYH. J. MCDONALD, L. R. ROTHSTEIN AND H. E. ROBISON gradually heated to 70 . After cooling to 10” the crystalline acid chloride was collected, at loo, and washed with Conant and Hussey’ have previously described 30-60‘ ligroin. The vacuum dried product weighed the reaction between several types of alkyl 2.7 g. A dry ethereal solution of glycine ethyl ester prechlorides and potassium iodide. We have pared by the method of Fixher* was standardized, by titration with standard acid, and the requisite amount of checked some of the results of these investigators this solution added to the dry acid chloride aFd the and have extended their procedure to certain mixture allowed to stand for sixteen hours a t 5 . The other alkyl halides. solid was collected, washed several times with water and We have found that there is no measurable re- dried in vacuo to give 1.7 g. of 11, colorless powder, m. p. 144-145’. The ethereal filtrate was washed with water, action between either &amyl chloride or i-butyl dilute hydrochloric acid, and again with water and dried chloride and potassium iodide after contact times first over anhydrous potassium carbonate and finally over of twenty-four hours a t temperatures up to 60’. Drierite. Evaporation of the dried s6lution gave an addiThe result obtained in the former case is not sur- tional 0.7 g. of I1 for a total yield of 2.4 g. (677,). Anal. Calcd. for CISHITO&IZ(609): C, 37.5; H,2.8; prising in view of the fact that tertiary alkyl halides in general are extremely unreactive. In N, 2.3. Found: C, 37.5; H, 3.0; N, 2.4. 3,5-Diiodo-4-(4’-hydroxyphenoxy) -hippuric Acid Monosuch second order substitution reactions, Conant’ (III).-To 2 g. of I1 was added 40 ml. of 1 N has shown the ease of substitution to be primary> hydrate sodium hydroxide in 50y0 ethanol and the suspension
secondary >tertiary. On this basis it is difficult to see why the primary alkyl halide, i-butyl chloride, should prove (1) Conant and Hussey T R I JOURNAL, ~ 47, 476 (1925)
(1) (a) C.R. Harington 8nd’G. BargCr, Biochcn. J . , Pi, 169 (1927); (b) C. Niemann and C. E. R e d e m a n n , THISJOURNAL, 69, 1549 (1941). (2) E. Fischer. Bcr.. S I , 433 (1901).
NOTES
Nov., 1944
1985
stirred for three hours at 25". The reaction mixture was filtered and the filtrate acidified with N hydrochloric acid. The precipitate was collected, washed, dried in wcuo, and reaystdized from 30% ethanol t t give 1.7 g. (93%) of 111, colorless needles, m. p. 186-187 Anal. Calcd. for C&llOrNI:.H:O (557): C, 32.4; H,2.4; N,2.5. Found: C.32.5; H,2.7; N, 2.3. 3,S-Diiodo4(3',5'-diiodo-4'-hydroxpphenoxy) -hippuric Acid (rv)-To 0.7 g. of 111, dissolved in 10 ml. of 15. N ammonium hydroxide, was added, slowly and with stirring, the requisite &mount of N potassium triiodide. When about half of the iodine had been added, the ammonium salt of IV separated in the form of glistening silvery leaflets. After all of the iodine had been added the solution was stirred for several minutes and allowed to stand at 5" for three to four hours. The suspension was decolorized with sodium metabisulfite and the free acid liberated by the addition of acetic acid. The precipitate was collected, washed with water, and dried in olkttlo to give 1.0 g. (97%) of IV, colorless crystalline powder, m. p. 248" with decomposition and evolution of iodine. After recrystallization from 70% ethanol IV was obtained as colorless leaflets, m. p. 248" with decomposition. Anal. Calcd. for cl&H$o&~4 (791): C, 22.8; H, 1.1; N, 1.8. Found: C, 22.8; H, 1.5; N, 1.8. CONTRIBUTION No. 984 FROM THE GATESAND CRELLIN LABOIUTORIES OF CHEXISTRY CALIFORNIA INSTITUTE OF TECHNOLWY PASADENA, CALIFORNIA ~ C E I V E DAUGUST 8, 1944
It may be noted that an interesting correlation exists between these absorption and fluonscence spectra of triphenylmethyl and the Raman spectra of substituted benzenes. The principal . Raman frequencies of substituted benzenes are 200, 400, 615, 1O00, 1165, 1595, and 3060 cpl.-'; all but the last (the carbon-hydrogen stretching frequency) are represented in the absorption and fluorescence spectra. The correlation is closest with monosubstituted benzenes containing a group conjugated with the benzene ring, such as methyl benzoate and benzaldehyde; Raman frequencies for benzaldehyde (other than the carbonyl frequency 1700 em.-') are given for comparison in Table I. There is a rough correlation in intensity as well as in frequency. The bands at 1850,2210, and 2510 may be combinations or overtones; they may well be combinations of the important frequency 1550 cm.-l with lower frequencies. The failure of the band with shift 3063 cm.-l to appear in the fluorescence spectrum may indicate that the coupling of this C-H vibration with the electronic transition is very weak. An interesting detail is the gradual change in shape of the absorption spectrum in the 100& The Light Absorption and Fluorescence of Tri- 1200 cm.-l region as the phenyl groups in the triphenylmethyl radical are successively replaced by arylmethyl Free Radicals p-t-butylphenyl groups. The band a t 1000 an.-' BY LINUSPAULINC gradually diminishes in intensity, and finally disBy working at low temperatures with triaryl- appears; the spectrum of tri-(p-t-butylphenyl) methyl free radicals frozen in a rigid glassy sol- methyl, which otherwise closely resembles that of vent, Lewis, Liplrin, and Magell have obtained triphenylmethyl, shows a single peak a t 1120em.-' absorption spectra and fluorescence spectra which in place of the 970-1080 doublet. This fact is show a striking vibrational fine structure, essen- without doubt related to the observed characteristially the same for absorption (determined by the tic absence of the lines near 10oO em.-' in the vibrational structure of the excited state) and Raman spectra of the para-disubstituted benzenes. I believe that measurements of well-resolved fluorescence (determined by the normal state); the authors report nine vibrational frequencies absorption spectra, fluorescence spectra, and phosfor the triphenylmethyl radical, and their repro- phorescence spectra of rigid solutions a t low temduced microphotometer records indicate one or peratures may provide much useful information about the vibrational frequencies of molecules of two more (Table I). dyes and other substances which could not be TABLEI readily obtained by the techni'ques of Raman and COMPARISON OF VIBRATIONAL WQUIENCIES infrared spectroscopy. Triphenylmethyl Absorptbon Fluorescence
190 (400)O 600 820 970 1090 1520
230 670 970 1080 1550
Benzaldehyde Reman
239 em-'. 439 615 827 1001 1164 1203 1597
CONTRIBUTION No. 993 FROM THE GATESAND CRkLLIN LABORATORIES OF CHEMISTRY CALIFORNIA INSTITUTE OF TECHNOLOGY PASADENA, CALIFORNIA RECEIVED OCTOBER4, 1944
The System Sodium Molybdate-Sodium Nitrate-Water and Part of the System Sodium Molybdate-Molybdic Oxide-Water, at 25' BY J. E. RICCIAND L. DOPPELT~
1850
The experimental procedure for these measurements was that described for similar investigations of ternary systems of salts and water. The 3063 materials used w e e c. P.products throughout, the e Estimated from the published microphotometer molybdic oxide being a very pure sample,2found record. 2210 2510
(1) PreKat addrras: U. S . Army. (2) This material, resublimed and of stated purity 09.9790. was the gift of the Climax Molybdenum Cornpay.
